CN106927554A - A kind of dendritic heavy metal chelating agent for having chelate for flocculation dual property concurrently and its application - Google Patents
A kind of dendritic heavy metal chelating agent for having chelate for flocculation dual property concurrently and its application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
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- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
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- C08G83/004—After treatment of dendrimers
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention relates to a kind of dendritic heavy metal chelating agent for having chelate for flocculation dual property concurrently and its application.The heavy metal chelating agent be by algebraically G for 1 ~ 3 polyamidoamine dendrimers(With PAMAM (NH2)8GRepresent, G is algebraically), the end dithiocar-bamate based polyamide amine dendritic for being reacted with carbon disulfide and being prepared.The end dithiocar-bamate based polyamide amine dendritic, because of its special three-D space structure, suitable molecular size range, highdensity end chelation group dithiocar-bamate, make it that not only there is strong chelating ability with heavy metal ion, and with heavy metal chelating after the deposition flco that is formed is big, it is fast, easily separated to settle, have efficient chelating concurrently with flocculation heavy metal energy.
Description
Technical field
The invention belongs to environmental protection technical field, and in particular to a kind of dendroid for having chelating-flocculation dual property concurrently
Polymer heavy metal chelating agent and its application, the heavy metal chelating agent are end chelation group dithiocar-bamate number
For 8G, (G is algebraically, G ≠ 0, the end dithiocar-bamate based polyamide-amine dendritic of G=1~3).
Background technology
Heavy metal containing wastewater treatment method mainly has chemical precipitation method, ion-exchange, hyperfiltration, active carbon adsorption, its
Middle chemical precipitation method advantage of lower cost, technique are relatively easy, technology is more ripe, therefore application is the most universal.
Traditional chemical precipitation method mainly has neutralization precipitation method, sulphide precipitation.
Neutralization precipitation method, is that addition alkaline chemical carries out neutralization reaction in the waste water of heavy metal, gives birth to heavy metal
Removed into water insoluble hydroxide precipitation.Although neutralization precipitation method cost is relatively low, there are some defects:(1) due to
Various heavy usually coexists in waste water, when containing amphoteric metals such as Zn, Pb, Sn, Al, precipitation, pH value is difficult when pH is relatively low
Amphoteric metal has redissolution to be inclined to when higher, needs accurate adjustment pH value, carries out fractional precipitation treatment, to ensure optimal removal effect
Really, making handling process becomes complex;(2) pH controls are bad, easily form colloid;(3) pH of processed waste water usually reaches
More than 10, it is necessary to can just be discharged after carrying out neutralisation treatment, acid and alkali consumption is higher;(4) complex state heavy metal can not be removed, needs to combine
Oxidation-reduction method carries out contact break pretreatment;(5) the hydroxide precipitation for producing, can cause with the reduction dissolution once again of pH value
Secondary pollution.
Sulphide precipitation is, in pH 9 or so, to add sulfide (vulcanized sodium, NaHS etc.) to give birth to heavy metal ion
Removed into water insoluble sulfide precipitation.Compared with neutralization precipitation method, heavy metal sulfide solubility is than its hydroxide
Solubility it is lower, heavy-metal residual is lower.But sulphide precipitation is tiny, sinking speed is slow, easy residual, the precipitation of residual
Meeting acid can generate hydrogen sulfide gas, produce secondary pollution.
The traditional chemical such as neutralization precipitation method, sulphide precipitation precipitation method process heavy metal wastewater thereby, are often difficult row up to standard
Put.
In view of the problem that the traditional chemical precipitation method are present, occurs in that dithiocar-bamate in recent years
(dithiocarbamate, hereinafter referred to as DTC) class organic heavy metal trapping agent precipitation method.DTC classes heavy metal chelating agent can be with weight
Metal forms water insoluble stability precipitation, and content of beary metal after treatment in water is far below traditional place of settling logos.
DTC classes heavy metal chelating agent is broadly divided into two classes by molecular structure:DTC class linear polymer type heavy metals trappings
Agent, DTC micromolecular heavy metal chelating agents.DTC class linear polymer type heavy metal chelating agents, are by linear polymer molecules
Amido on chain is grafted dithionate and is formed.Such as polyethyleneimine (Chinese invention patent CN 101081827A), poly- third
The grafting two such as acrylamide (Chinese invention patent CN 101979416B), starch (Chinese invention patent CN 101759809B) is thio
Carboxylate and form DTC class linear polymeric polymer heavy metal chelating agents.DTC micromolecular heavy metal chelating agents, are by small
Molecule amine compound is grafted dithionate.Such as ethylenediamine (Chinese invention patent CN 101857296B), piperazine (China
The B of patent of invention CN 102216410), the grafting carbodithioic acid such as melamine (A of Chinese invention patent CN 103224472)
Salt and form DCT small molecule heavy metal chelating agents.
The flocculation of DTC class linear polymer heavy metal chelating agents and settling property are preferable, but linear polymer molecules chain is easy
In curling, especially under acid and neutrallty condition, DTC groups is hidden in inside strand, reduce DTC groups with a huge sum of money
The sequestration efficiency of category.Small molecule DTC class heavy metal chelating agents, although the sequestration efficiency with heavy metal is high, but the chelating for being formed
Body deposition is tiny, sinking speed is slow, it is necessary to add flocculant and reach rapid subsidence purpose.Therefore have chelating concurrently and flocculate dual
The heavy metal chelating agent of performance turns into the active demand of current heavy metal treatment.
Dendritic is used as the new three-dimensional polymer of a class in recent years, compared with linear polymer, with accurate
Molecular structure, the geometrical symmetry of height, peripheral substantial amounts of functional group, intramolecular exist cavity, relative molecular mass can
Control property, molecule have the architectural characteristics such as nano-scale in itself.Polymer polyamide-amine (PAMAM) is used as dendritic
Represent, increasingly attract much attention, in view of the whole generation products of PAMAM both have substantial amounts of amine end, and with rigidity not
The characteristic for easily crimping, therefore can the new DTC class dendritic heavy metal chelating agents of scion grafting dithionate one class of formation.
The present inventor discloses a kind of 0 generation of dithionate's functionalization polyamide in patent of invention CN103864654B
Amine --- end dithiocar-bamate base 0 generation daiamid.The polymer has the plane quadrilateral structure of two dimension, relative to
DTC micromolecular heavy metal chelating agents, floc particle is big, and flocculation sediment performance is greatly improved, but flco density is not high.Sedimentation speed
Degree is not as good as DTC class linear polymer heavy metal chelating agents.
The content of the invention
Drawbacks described above it is an object of the invention to overcome existing DTC classes heavy metal chelating agent, there is provided one kind has DTC concurrently
The sequestration efficiency of micromolecular heavy metal chelating agent is high, DTC class linear polymer heavy metal chelating agents sedimentation is quick etc. both
The heavy metal chelating agent for having chelating-flocculation dual property concurrently of advantage.
To achieve the above object, the heavy metal chelating agent for having chelating-flocculation dual property concurrently that the present invention is provided, by one kind
With space three-dimensional structure, end dithiocar-bamate (DTC) number be 8G (G algebraically, G ≠ 0, G=1's~3)
Hold dithiocar-bamate based polyamide amine dendrimers (PAMAM- (NHCSSNa)8G, with PAMAM- (DTC)8GRepresent),
Its structure is shown in formula I:
Wherein:" A " represents core:Alkylenediamine [N (CH2)2~12N];" ━ " represents side chain:
[CH2CH2CONHCH2CH2];" N " represents interior branch atom:Nitrogen-atoms;" G " representation algebra:It is the positive integer between 1~3.
In the present invention, the structure is the end dithiocar-bamate based polyamide amine dendrimers polymerization of formula I
Thing, is (below with PAMAM- (NH by polyamide-amide that the algebraically G of general formula II is 1~32)8GRepresent, G ≠ 0, G=1~
3) prepared for raw material and carbon disulfide react.
Wherein:" A " represents core:Alkylenediamine [N (CH2)2~12N];" ━ " represents side chain:
[CH2CH2CONHCH2CH2];" N " represents interior branch atom:Nitrogen-atoms;" G " representation algebra:It is the positive integer between 1~3.
In the present invention, the specific preparation process of the end dithiocar-bamate based polyamide-amine dendritic
It is as follows:
(1) addition reaction:By the daiamid (PAMAM- (NH that algebraically G is 1~32)8G, G ≠ 0, the methyl alcohol of G=1~3)
Solution is added in reactor, leads to nitrogen, is cooled to 5~10 DEG C.The methanol solution of excessive carbon disulfide is slowly added dropwise, is controlled
Rate of addition, makes reaction mixture temperature be 5~10 DEG C.After completion of dropping, 25 DEG C are warming up to, reacted 1~5 hour, there is white
Precipitation, filtering obtains the dithiocarbamate-based daiamid in the end (PAMAM- (NHCSSH) of white8G), mother liquor is first
The mixed solution of alcohol and unreacted carbon disulfide, can be back to addition reaction next time.
(2) salt-forming reaction:Dithiocarbamate-based daiamid (the PAMAM- in end that step (1) is obtained
(NHCSSH)8G) be added in reactor, sodium hydrate aqueous solution is added, in being reacted 1~3 hour at 40~60 DEG C, obtain end two
Wherein:Mol ratio PAMAM- (the NH of reactant2)8G:CS2:NaOH=1:(20G~30G):(6G~8G).
Reaction equation is as follows:
Algebraically G used by embodiment in the present invention is 1~3 polyamide-amide (G ≠ 0, G=1~3), purchased from sigma-
Aldrich Chinese companies;Carbon disulfide, NaOH, methyl alcohol used, is commercially available product.
Obtained end dithiocar-bamate base algebraically G of the invention is 1~3 Polyamidoamine Dendrimers
(PAMAM-(DTC)8G, G ≠ 0, G=1~3), being deposited with the flock that is precipitated as that heavy metal is formed, particle volume is big, closely knit, heavy
Drop is fast, easily separated, while showing highly effective chelating heavy metal ability, has the performance of flocculation sediment heavy metal concurrently.
The inventors discovered that, by 0 PAMAM (PAMAM- (NH2)4, G=0) prepare end dithiocar-bamate
Based polyamide amine (PAMAM- (DTC)4), with heavy metal formed flco deposition, be sheet deposition, but loose, sedimentation rate compared with
Slowly.
The inventors discovered that, by G >=4 polyamide-amide (PAMAM- (NH2)8G) prepare end dithiocar-bamate base
Daiamid (PAMAM- (DTC)8G), although the flco deposition formed with heavy metal, particle is big, sedimentation rate is fast, but due to it
Preparation cost is higher, and application value is little.
End dithiocar-bamate based polyamide amine dendrimer (PAMAM- (DTC) provided by the present invention8G(G generations
Number, G ≠ 0, G=1~3), because of its special space three-dimensional structure, highdensity end group chelation group dithiocar-bamate
(DTC), make it has very strong adhesion with heavy metal, improves the sequestration efficiency to heavy metal ions in wastewater, can be with weight
The cotton-shaped deposition that volume is big, closely knit, deposition velocity is fast that metal is produced, shortens the sedimentation time, makes the weight of the residual in waste water
Concentration of metal ions is reached below the discharge standard of national regulation, is not likely to produce secondary pollution, and the trapping agent is also recyclable water-soluble
Precious metal in liquid, and have the advantages that addition is few, sequestration efficiency is high.
End dithiocar-bamate based polyamide-amine dendrimer (PAMAM- (DTC) provided by the present invention8G, G
The industry waste water such as ≠ 0, G=1~3) can be used for are electroplated, the manufacture of circuit board, film, metal finishing, battery production, coal-fired plant
Treatment, it can also be used to which industry and the treatment of domestic garbage incineration flyash heavy metal stabilization, and heavy metal pollution farmland stabilize and repaiies
It is multiple.
Specific embodiment
Technical scheme is described in further detail below in conjunction with specific embodiment.Specific embodiment contributes to this
The understanding and implementation of invention, protection scope of the present invention are not limitation with specific embodiment, and are limited with claim
It is fixed.
Comparative example:Hold the preparation of dithiocar-bamate base 0G PAMAMs
To equipped be slowly added in agitator, condenser pipe, thermometer, the four-neck flask of dropping funel 129.17g (20%,
0.05mol) 0 PAMAM (the Ethylenediamine core, 0generation, PAMAM of ethylenediamine core
dendrimer;M516.68, following shorthand PAMAM- (NH2)4) methanol solution, be cooled to 5 DEG C, be slowly added dropwise 60.91g
The methanol solution of (50%, 0.40mol) carbon disulfide (M76.14), controls rate of addition, makes the reaction mixture temperature be<10
DEG C, 25 DEG C are warming up to after completion of dropping, react 4 hours, there is white precipitate to separate out, to filter, 60 DEG C of drying are obtained in the middle of 40.87g
The dithiocarbamate-based daiamid of body end (PAMAM- (NHCSSH)4), M821.24).The intermediate PAMAM- that will be obtained
(NHCSSH)4Four-neck flask is all added, 33.50g water, the sodium hydroxide solution of 20.00g (40%, 0.20mol) is added, in
Reacted 2 hours at 50 DEG C, obtain solid content and be about 50% end dithiocar-bamate based polyamide amine (with PAMAM- (DTC)4
Represent).Its structure is as follows:
Embodiment 1:Hold the preparation of dithiocar-bamate base 1G daiamid dendritic macromoles
To equipped be slowly added in agitator, condenser pipe, thermometer, the four-neck flask of dropping funel 143.00g (20%,
0.02mol) 1 generation daiamid (the Ethylenediamine core, 1generation, PAMAM of ethylenediamine core
dendrimer;M1429.85, following shorthand PAMAM- (NH2)8) methanol solution, be cooled to 5 DEG C, be slowly added dropwise 60.91g
The methanol solution of (50%, 0.40mol) carbon disulfide (M76.14), controls rate of addition, makes the reaction mixture temperature be<10
DEG C, 25 DEG C are warming up to after completion of dropping, react 2 hours, there is white precipitate to separate out, to filter, drying obtains 40.76g ends two thio
Carbamic acid based polyamide amine (PAMAM- (NHCSSH)8), M2018.97), yield 99.95% illustrates end amido (with-NH2Meter)
It is (- NH with the carbon disulfide mol ratio for participating in reaction2):(CS2)=1:1.Mother liquor be methyl alcohol and unreacted carbon disulfide, can
Reuse.
By the PAMAM- (NHCSSH) of gained8Add four-neck flask, add 35.00g water, 16.00g (40%,
Sodium hydroxide solution 0.16mol), in being reacted 2 hours at 50 DEG C, obtains solid content and is about 50% end dithiocar-bamate
Based polyamide amine is (with PAMAM- (DTC)8Represent).
Gained PAMAM- (DTC)8Nuclear magnetic resoance spectrum (13C NMR):33.23、33.45、37.33、39.68、42.28、
52.98th, 53.22,55.98,56.02,174.56,175.92,212.25ppm, its structure is as follows:
Embodiment 2:Hold the preparation of dithiocar-bamate base 2G daiamid dendritic macromoles
To equipped be slowly added in agitator, condenser pipe, thermometer, the four-neck flask of dropping funel 162.81g (20%,
0.01mol) 2 generation daiamids (the Ethylenediamine core, 2generation, PAMAM of ethylenediamine core
dendrimer;M3256.18, following shorthand PAMAM- (NH2)16) methanol solution, be cooled to 5 DEG C, be slowly added dropwise 73.09g
The methanol solution of (50%, 0.48mol) carbon disulfide (M76.14), controls rate of addition, makes the reaction mixture temperature be<10
DEG C, 25 DEG C are warming up to after completion of dropping, react 4 hours, there is white precipitate to separate out, to filter, 60 DEG C of drying are obtained in the middle of 44.71g
The dithiocarbamate-based daiamid of body end (PAMAM- (NHCSSH)16), M4474.42), yield 99.93%.Mother liquor is first
The mixed solution of alcohol and unreacted carbon disulfide, can reuse.
The intermediate PAMAM- (NHCSSH) that will be obtained16Four-neck flask is all added, 42.00g water, 16.00g is added
The sodium hydroxide solution of (40%, 0.16mol), in being reacted 2 hours at 50 DEG C, obtains solid content and is about 50% end dithiocarbamates
Formates based polyamide amine is (with PAMAM- (DTC)16Represent).
Gained PAMAM- (DTC)16Nuclear magnetic resoance spectrum (13C NMR):33.36、33.56、33.84、37.38、39.61、
39.78、42.42、51.98、52.93、52.96、55.32、55.76、56.63、175.46、175.89、176.22、
212.75ppm, its structure is as follows:
Embodiment 3:Process circuit plate heavy metal wastewater thereby
Certain board wastewater:pH 2.6、Cu2+165.282mg·L-1、Ni2+101.395mg·L-1, add embodiment 1,2
And the heavy metal chelating agent of comparative example, 5min is stirred, 5min is precipitated, filtering, check weighing metal concentration the results are shown in Table 1.
Result shows, dosage 200mgL-1When, the PAMAM- (DTC) of embodiments of the invention 1,28、PAMAM-
(DTC)16, can reach " copper, cobalt, nickel industrial pollution source discharge standard (GB25467-2010) " and " town-sewage discharge mark
The emission request of accurate (GB18918-2002) ", and comparative example PAMAM- (DTC)4Do not reach then.Comparative example PAMAM- (DTC)4Need
Want 250mgL-1When, the requirement of " copper, cobalt, nickel industrial pollution source discharge standard (GB25467-2010) " is can reach, but do not reach
The requirement of " town-sewage discharge standard (GB18918-2002) ".
From the point of view of the form for forming deposition with heavy metal, the PAMAM- (DTC) of embodiments of the invention 1,28、PAMAM-
(DTC)16, with heavy metal formed flco deposited particles are big, closely knit, sinking speed is fast.And comparative example PAMAM- (DTC)4, with weight
Although the deposition volume that metal is formed is big, although volume is big, and loose, sedimentation rate is slower.
Cu, Ni content after the before processing of table 1
Embodiment 4:Certain lead waste water containing complex state
Certain EDTA complex state lead waste water:pH 2.26、Pb2+50.02mg·L-1, add embodiment 1 and be prepared by comparative example
Heavy metal chelating agent, stir 5min, precipitate 5min, filtering, check weighing metal concentration the results are shown in Table 2.
Result shows, the PAMAM- (DTC) of embodiment 18Dosage 150mgL-1When, can reach GB " GB25467-
2010 " and " GB18918-2002 " emission request.And comparative example PAMAM- (DTC)4Need 200mgL-1When, can reach state
The requirement of " GB25467-2010 " is marked, but does not reach the requirement of GB " GB18918-2002 ".
Simultaneously it is observed that the PAMAM- (DTC) of embodiment 18, sinking speed big, closely knit with the precipitation volume of lead formation
Hurry up.The PAMAM- (DTC) of comparative example4The precipitation formed with lead, although volume is big but loose slabbing, sinking speed relatively
Slowly.
Due to the PAMAM- (DTC) of more than 1.0G8End has 8 end groups, is a kind of dendroid of space three-dimensional structure
Macromolecular, therefore the larger chelating body deposition of network structure can be formed with heavy metal, sinking speed is fast.And the PAMAM- of 0G
(DTC)4, end has 4 end groups, is a kind of star-like super-branched compound of planar structure, therefore can be with heavy metal shape
Into chelating body be planar structure, although volume is big, but sinking speed is relatively slow.
Cu, Ni content after the before processing of table 2
Claims (4)
1. a kind of dendritic heavy metal chelating agent for having chelating-flocculation dual property concurrently, it is characterised in that the huge sum of money
Category trapping agent is to hold dithiocar-bamate based polyamide-amine dendritic, its end chelation group dithiocarbamates
The number of formates is that (G ≠ 0, G=1~3), structural formula is represented by formula I to 8G:
Wherein:" A " represents core:Specially Alkylenediamine [N (CH2)2~12N];" ━ " represents side chain:Specially
[CH2CH2CONHCH2CH2];" N " represents interior branch atom:Specially nitrogen-atoms;" G " representation algebra:Between specially 1~3
Positive integer.
2. heavy metal chelating agent according to claim 1, it is characterised in that the end dithiocar-bamate base polyamides
Amine amine dendritic is that for 8G, (G ≠ 0, the daiamid of G=1~3) is raw material and curing by the number of terminal amido
What carbon reacted and prepared, (G ≠ 0, the structural formula of daiamid of G=1~3) is the institute of formula II for 8G for the number of the terminal amido
Show:
Wherein:" A " represents core:Specially Alkylenediamine [N (CH2)2~12N];" ━ " represents side chain:Specially
[CH2CH2CONHCH2CH2];" N " represents interior branch atom:Specially nitrogen-atoms;" G " representation algebra:Between 1~3
Positive integer.
3. a kind of application of heavy metal chelating agent as claimed in claim 1, it is characterised in that institute's dendritic is used as a huge sum of money
Category trapping agent is applied to the heavy metals removal in heavy metal wastewater thereby, acid heavy metal wastewater or complex state heavy metal wastewater thereby.
4. a kind of application of dendritic as claimed in claim 1, it is characterised in that the dendritic is used as weight
Metallic stabilizer, is applied to heavy metal stabilization treatment and Heavy Metals in Contaminated Soils stabilization reparation in incineration of refuse flyash.
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US15/936,433 US20180215636A1 (en) | 2017-03-31 | 2018-03-27 | Dendritic polymer heavy metal precipitant with double functions of chelation and self-flocculation and its application |
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